Cyclopropanecarboxylic acid-phenoxy-α-vinyl-benzyl esters, processes for producing them, and their use in combating pests

ABSTRACT

Cyclopropanecarboxylic acid-phenoxy-α-vinyl-benzyl esters of the formula ##STR1## in which Y is chlorine or bromine, and R 1  is --CH═CH 2  or ##STR2## processes for producing them, and their use in combating pests.

RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.955,667, filed Oct. 27, 1978 now abandoned.

The present invention relates to cyclopropanecarboxylicacid-phenoxy-α-vinyl-benzyl esters, to processes for producing them, andto their use in combating pests.

The cyclopropanecarboxylic acid esters have the formula ##STR3## inwhich Y is chlorine or bromine, and R₁ is --CH═CH₂ or ##STR4##

The compounds of the formula I are produced by methods known per se, forexample as follows: ##STR5##

In the formulae II to VI, the symbols R₁ and Y have the meanings givenunder the formula I.

X in the formulae III and IV is a halogen atom, particularly chlorine orbromine, and R in the formula VI is C₁ -C₄ -alkyl, especially methyl orethyl. Suitable acid-binding agents for the processes 1 and 2 are inparticular tertiary amines, such as trialkylamine and pyridine, alsohydroxides, oxides, carbonates and bicarbonates of alkali metals andalkaline-earth metals, and also alkali metal alkoholates, such aspotassium-t-butylate and sodium methylate. The water-binding agent usedfor the process 3 can be for example dicyclohexylcarbodiimide. Theprocesses 1 to 4 are performed at a reaction temperature between -10°and +120° C., usually between 20° and 80° C., under normal or elevatedpressure, and preferably in an inert solvent or diluent. Suitablesolvents or diluents are for example: ethers and ethereal compounds suchas diethyl ether, dipropyl ether, dioxane, dimethoxyethane andtetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides;aliphatic, aromatic as well as halogenated hydrocarbons, especiallybenzene, toluene, xylene, chloroform and chlorobenzene; nitriles such asacetonitrile: dimethylsulfoxide and ketones such as acetone and methylethyl ketone.

The starting materials of the formula II, IV and VI are known and can beproduced by methods analogous to known methods. Disclosures relating tosuch starting materials may, for example, be found in DOS No. 2,142,546.The preparation of starting materials III and V is describedhereinafter.

Unless homogeneous optically active starting materials are used in theproduction process, the compounds of the formula I are obtained asmixtures of various optically active isomers. The different isomericmixtures can be separated by known methods into the individual isomers.By `compound of the formula I` is meant both the individual isomers andmixtures thereof.

The compounds of the formula I are suitable for combating various animaland plant pests. They are suitable in particular for combating insectsand phytopathogenic mites and ticks, for example of the ordersLepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina,Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura,Isoptera, Psocoptera and Hymenoptera.

Compounds of the formula I are especially suitable for combating insectswhich damage plants, particularly insects which damage plants by eating,in crops of ornamental plants and useful plants, especially in cottoncrops, (for example against Spodoptera littoralis and Heliothisvirescens) and in crops of vegetables (for example against Leptinotarsadecemlineate and Myzus persicae). The active substances of the formula Ialso exhibit a very favourable action against flies, such as Muscadomestica, and against mosquito larvae.

The acaricidal and insecticidal action can be substantially broadenedand adapted to suit given circumstances by the addition of otherinsecticides and/or acaricides. Suitable additives are, for example,organic phosphorus compounds, nitrophenols and derivatives thereof,formamidines, ureas, other pyrethrin-like compounds, and also carbamatesand chlorinated hydrocarbons.

Compounds of the formula I are combined particularly advantageously alsowith substances which have a synergistic or intensifying effect onpyrethroids. Examples of such compounds are, inter alia,piperonylbutoxide, propynyl ethers, propynyl oximes, propynyl carbamatesand propynyl phosphonates,2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex orSesoxane), S,S,S-tributylphosphorotrithioates and1,2-methylenedioxy-4-(2-octylsulfonyl)-propyl)-benzene.

Compounds of the formula I can be used on their own or together withsuitable carriers and/or additives. Suitable additives can be solid orliquid and they correspond to the substances common in formulationpractice, such as natural or regenerated substances, solvents,dispersing agents, wetting agents, adhesives, thickeners, binders and/orfertilisers.

The compositions according to the invention are produced in a mannerknown per se by the intimate mixing and/or grinding of the activesubstances of the formula I with suitable carriers, optionally with theaddition of dispersing agents or solvents which are inert to the activesubstances. The active substances can be obtained and used in thefollowing forms:

solid preparations: dust, scattering agents, granules (coated granules,impregnated granules and homogeneous granules);

liquid preparations:

(a) water-dispersible concentrates of active substance: wettablepowders, pastes or emulsions;

(b) solutions.

The content of active substance in the compositions described is between0.1 and 95%, it is to be mentioned in this respect that with applicationfrom an aeroplane, or by other suitable devices, concentrations of up to99.5% or even the pure active substance can be used.

The active substances of the formula I can be formulated for example asfollows (parts are by weight):

DUSTS

The following substances are used to produce (a) a 5% dust and (b) a 2%dust:

    ______________________________________                                        (a)      5     parts of active substance, and                                          95    parts of talcum;                                               (b)      2     parts of active substance,                                              1     part of highly dispersed silicic acid, and                              97    parts of talcum.                                               ______________________________________                                    

The active substance is mixed and ground with the carriers.

GRANULATE

The following ingredients are used to produce a 5% granulate:

    ______________________________________                                        5        parts of active substance,                                           0.25     part of epichlorohydrin,                                             0.25     part of cetyl polyglycol ether,                                      3.50     parts of polyethylene glycol, and                                    91       parts of kaolin (particle size 0.3-0.8 mm).                          ______________________________________                                    

The active substance is mixed with epichlorohydrin and dissolved in 6parts of acetone, and the polyethylene glycol and cetyl polyglycol etherare then added. The solution obtained is sprayed onto kaolin and theacetone is subsequently evaporated off in vacuo.

WETTABLE POWDERS

The following constituents are used to produce (a) a 40%, (b) and (c) a25%, and (d) a 10% wettable powder:

    ______________________________________                                        (a)   40     parts of active substance,                                             5      parts of sodium lignin sulphonate,                                     1      part of sodium dibutyl-naphthalene sulphonate, and                     54     parts of silicic acid;                                           (b)   25     parts of active substance,                                             4.5    parts of calcium lignin sulphonate,                                    1.9    parts of Champagne chalk/hydroxyethyl cellulose                               mixture (1:1),                                                         1.5    parts of sodium dibutyl-naphthalene sulphonate,                        19.5   parts of silicic acid,                                                 19.5   parts of Champagne chalk, and                                          28.1   parts of kaolin;                                                 (c)   25     parts of active substance,                                             2.5    parts of isooctylphenoxy-polyoxyethylene-ethanol,                      1.7    parts of Champagne chalk/hydroxyethyl cellulose                               mixture (1:1),                                                         8.3    parts of sodium aluminum silicate,                                     16.5   parts of kieselguhr, and                                               46     parts of kaolin;                                                 (d)   10     parts of active substance,                                             3      parts of a mixture of the sodium salts of                                     saturated fatty alcohol sulphates,                                     5      parts of naphthalenesulphonic acid/formaldehyde                               condensate, and                                                        82     parts of kaolin.                                                 ______________________________________                                         The active substance is intimately mixed in suitable mixers with the     additives, and the mixtures is then ground in the appropriate mills and     rollers to obtain wettable powders which can be diluted with water to give     suspensions of the desired concentration.

EMULSIFIABLE CONCENTRATES

The following substances are used to produce (a) a 10%, (b) a 25% and(c) a 50% emulsifiable concentrate:

    ______________________________________                                        (a)    10     parts of active substance,                                             3.4    parts of epoxidised vegetable oil,                                     3.4    parts of a combination emulsifier consisting of                               fatty alcohol polyglycol ether and alkylaryl-                                 sulphonate calcium salt,                                               40     parts of dimethylformamide, and                                        43.2   parts of xylene;                                                (b)    25     parts of active substance,                                             2.5    parts of epoxidised vegetable oil,                                     10     parts of an alkylarylsulphonate/fatty alcohol                                 polyglycol ether mixture,                                              5      parts of dimethylformamide, and                                        57.5   parts of xylene;                                                (c)    50     parts of active substance,                                             4.2    parts of tributylphenol-polyglycol ether,                              5.8    parts of calcium-dodecylbenzenesulphonate,                             20     parts of cyclohexanone, and                                            20     parts of xylene.                                                ______________________________________                                    

Emulsions of the concentration required can be prepared from theseconcentrates by dilution with water.

SPRAY

The following constituents are used to produce (a) a 5% spray and (b) a95% spray:

    ______________________________________                                        (a)     5     parts of active substance,                                              1     part of epichlorohydrin, and                                            94    parts of ligroin (boiling limites 160°-190°                     C.),                                                            (b)     95    parts of active substance, and                                          5     parts of epichlorohydrin.                                       ______________________________________                                    

The invention is further illustrated by the following Examples.

EXAMPLE 1 Manufacture of 3-phenoxy-α-(1',2'-dibromovinyl)benzylalcohol.

(a) With stirring and in a nitrogen atmosphere, 150 ml tetrahydrofuranin which 12-14 g/h acetylene was introduced were added successively (in3 hours) to a suspension of ethylmagnesia-bromide (produced with 30 gethylbromide and 6 g magnesia).

The resulting solution of ethynylmagnesia-bromide was cooled to 0° C.and then added dropwise to a solution of 35.8 g 3-phenoxy-benzaldehydein 25 ml tetrahydrofuran.

After 8 hours stirring at room temperature, the reaction solution wasadded dropwise to 750 ml of a saturated ammoniachloride solution. After30 minutes stirring the organic phase was separated, dried with sodiumsulfate and chromatographed over silicagel with hexan and ether 4:1 asdiluent.

There was obtained 24 g of the compound of the formula ##STR6## having arefractive index of n_(D) ³²° =1.5798.

(b) With stirring and under skylight lighting, 16 g bromine in 20 mlCCl₄ were added successively (in 2 hours) at a temperature of 10° to 20°C. to a solution of 22.4 g 3-phenoxy-α-(ethynyl)-benzylalcohol in 80 mlCCl₄.

After stirring for 10 hours at room temperature, the CCl₄ was distilledoff.

There was obtained the compound of the formula ##STR7## having arefractive index of n_(D) ³⁵° =1.6210.

Manufacture of 3-phenoxy-α-vinyl-benzylalcohol.

With stirring, at room temperature and under normal pressure, hydrogenwas introduced (3.37 l H₂ ; 0° C./760 mm Hg) in a solution of 33.73-phenoxy-α-ethynylbenzylalcohol in 340 ml dioxan and 1.7 g Lindlarcatalysator.

After filtration and dilution with water the product was extracted withether. After drying of the ether extracts with sodium sulfate andevaporation of the ether, the product was chromatographed over silicagelwith hexan and ether 1:1 as eluent.

There was obtained the compound of formula ##STR8## having a refractiveindex of n_(D) ³²° =1.5832.

Production of2,2-dimethyl-3-(1-bromo-2,2-dichloro-2-bromoethyl)-cyclopropanecarboxylicacid-3-(phenoxy)-α-vinyl-benzyl ester

3.2 g of pyridine in 10 ml of benzene is added dropwise at 5° C., withstirring, to 8 g of 3-phenoxy-α-vinyl-benzyl alcohol in 30 ml ofbenzene. After the addition of 14 g of2,2-dimethyl-3-(1-bromo-2,2-dichloro-2-bromoethyl)-cyclopropanecarboxylicacid chloride at 10° C., the mixture is stirred for 2 hours at roomtemperature, and is allowed to stand for a further 10 hours at thistemperature. The reaction mixture is diluted with ice water; the organiclayer is extracted three times with 100 ml of 3% HCl each time, andsubsequently three times with 100 ml of 3% sodium bicarbonate each time;the organic phase is dried with sodium sulfate, and the benzene isdistilled off. There is obtained the compound of the formula ##STR9## ascolourless oil having a refractive index of n_(D) ⁴⁰° =1.5776. In ananalogous manner is also obtained the compound of the formula ##STR10##

EXAMPLE 2 (A) Insecticidal stomach-poison action

Cotton plants were sprayed with a 0.05% aqueous emulsion of the activesubstance (obtained from 10% emulsifiable concentrate).

After drying of the coating, larvae of Spodoptera littoralis in the L₃-stage and of Heliothis virescens in the L₃ -stage were placed onto thecotton plants. The test was carried out at 24° C. with 60% relativehumidity.

Compounds according to Example 1 exhibited in the above test a goodinsecticidal stomach-poison action against larvae of Spodopteralittoralis and Heliothis virescens.

EXAMPLE 3 Acaricidal action

Phaseolus vulgaris plants were infested, 12 hours before the test foracaricidal action, with an infested piece of leaf from a mass culture ofTetranychus urticae. The transferred mobile stages were sprayed with theemulsified test preparations from a chromatography-sprayer in a mannerensuring no overflow of the spray liquor. An assessment was made after 2and 7 days, by examination under a binocular microscope, of the livingand of the dead larvae, adults and eggs, and the results were expressedas percentages. The treated plants were kept during the "holding time"in greenhouse compartments at 25° C.

Compounds according to Example 1 exhibited in the above test a goodaction against adults, larvae and eggs of Tetranychus urticae.

EXAMPLE 4 Action against ticks

(A) Rhipicephalus bursa

For each concentration, 5 adult ticks and 50 tick larvae, respectively,were counted into a small glass test tube, and immersed for 1 to 2minutes in 2 ml of an aqueous emulsion from a dilution series of 100,10, 1 and 0.1 ppm of test substance. The tubes were then sealed with astandardised cotton plug, and inverted so that the active-substanceemulsion could be absorbed by the cotton wool.

The evaluation in the case of the adults was made after 2 weeks and inthe case of the larvae after 2 days. There were two repeats for eachtest.

(B) Boophilus microplus (larvae) With a dilution series analogous tothat of Test A, tests were carried out with 20 sensitive larvae andOP-resistant larvae, respectively (resistance is with respect todiazinon compatibility).

Compounds according to Example 1 were effective in these tests againstadults and larvae of Rhipicephalus bursa and against sensitive andOP-resistant larvae, respectively, of Boophilus microplus.

We claim:
 1. A compound of the formula ##STR11## in which Y is chlorineor bromine, and R₁ is --CH═CH₂ or ##STR12##
 2. The compound according toclaim 1 of the formula ##STR13##
 3. The compound according to claim 1 ofthe formula ##STR14##
 4. An insecticidal and acaricidal compositioncomprising an insecticidally and acaricidally effective amount of acompound according to claim 1, together with a suitable carriertherefor.
 5. A method for combatting insects and acarids which comprisesapplying thereto or the locus thereof an insecticidally and acaricidallyeffective amount of a compound according to claim 1.